Metallizable disazo dyestuffs



METALLIZABLE DISAZO DYESTUFFS Rudolf Diirig, Basel, and Ernst Keller, Binningen, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm No Drawing. Application September 13, 1954, Serial No. 455,746

6 Claims. (Cl. 260-153) is diazotised and coupled in an alkaline medium with an azo component of the general Formula II In these formulae: R represents a benzene radical which contains the hydroxyl and the carboxyl group in the o-positions, X represents the direct simple linkage or a bridging member of the formula -CO-Ph-, --NHCO-Ph, Y represents hydrogen or the sulphonic acid group, Q represents a bridging member of the formula -NH, ---NH-CO-, -NHCONH-,

HOaS

Ph represents an mor p-phenylene radical which can be further substituted, Cy represents a 1.3.5-triaszinyl radical, Z1 represents an organically substituted amine radical, and Z2 represents a halogen atom, a hydroxyl group and advantageously if desired an organically substituted amine radical.

If desired, all the benzene rings in these formulae can be further substituted with substituents usual in azo dyestuffs, e. g. with halogen, alkyl, alkoxy, carboxyl and sulphonic acid groups.

The aminomonoazo dyestufis usable according to the present invention are obtained from amino-Z-hydroxybenzene-l-carboxylic acids, e. g. from or 3-amino- Z-hydroxybenzene-l-carboxylic acid, 5- (or 3-) amino- 2-hydroxybenzene-1-carboxylic-3- (or -5-) sulphonic acid, 5-amino-3-chloroor -3-methyl-2-hydroxybenzenel-carboxylic acid, by diazotising and coupling with l-amino-Z-carboxy-methoxy-naphthalene. 1-amino-2-carboxy-methoxy-naphthalene can be sulphonated in the 6- or 7-position. Instead of the amino-2- If desired, the

2,780,619 Patented Feb. 5, 1957 hydroxybenzene-l-carboxylic acids which are preferred, also aminobenzoyl derivatives of Z-hydroxybenzene carboxylic acids or of amino-Z-hydroxybenzene carboxylic acids can be used, in which case the amino group should be in the mor p-position with regard to the bridging member, to the o-hydroxybenzene carboxylic acid radical. The following compounds for example can be used: 3'- or 4'-amino-4-hydroxybenzophenone-S-carboxylic acid, 3- or 4-amino-3-methyl-4-hydroxybenzophenone-3-carboxylic acid, 3'-amino-4'-methyl-4-hydroxybenzophenone-S-carboxylic acid, also 3- or 4-aminobenzoyl, 3-amino-4-methyl-benzoyl, 3-amino-4-chlorobenzoyl, 3-amino-4-methoxybenzoyl derivatives of the amino- 2-hydroxybenzene-1-carboxylic acids listed above, and also 3- or 5-(3'-aminobenzoylamino)-2-hydroxybenzenel-carboxylic acid-4'-sulphonic acids. The coupling with the 1-amino-2-carboxy-methoxy-naphthalene or its 6- or 7-sulphonic acids is performed in an acid medium and the diazotisation of the monoazo dyestutf is performed according to the usual indirect method with sodium nitrite and mineral acid in the cold. It is of advantage to choose the components of the monoazo dyestufi so that it contains a sulphonic acid group.

Starting material for the coupling components of the general Formula H usable according to the present invention are those derivatives of 2amino-5-hydroxynaphthalene-7-sulphonic acid which contain an mor p-aminophenyl radical bound either direct to the amino group or, if desired, bound by way of bridging members which can also form parts of an azole ring which is fused to the naphthalene ring. Such derivatives are for example: 2 (4' aminophenylamino) 5 hydroxynaphthalene- 7-sulphonic acid, 2-(4- amino 3'- carboxyphenylarnino)- S-hydroxynaphthalene-7-sulphonic acid, 2-(3- or 4'- aminobenzoylamino) 5 hydroxynaphthalene 7 sulphonic acid, 2-(4-chloroor -methyl-3'-aminobenzoylamino)-5-hydroxynaphthalene-7-sulphonic acid, 2-(4'- aminophenyl ureido) 5 hydroxynaphthalene 7 sulphonic acid, 2 (3 or .4'- aminophenyl) 5"- hydroxy- 4.5:l".2-naphthothiazole-7"-sulphonic acid. By reacting the alkali salts of these compounds in aqueous solution with finely distributed cyanuric chloride in the cold according to methods known per se and by the gradual replacement at a raised temperature of a further halogen atom of the condensation product by an organic amine and preferably, of both halogen atoms by amines of the benzene series, the coupling components which can be used according to the present invention are obtained.

The diazotised monoazo dyestuif is coupled with the end components of the general Formula II in an alkaline medium, if desired with the addition of agents which Ifjacilitate the coupling such as pyridine or alkanolamine ases.

In the form of their alkali salts, the diazo dyestuffs according to the present application are dark powders which dissolve in hot water with a pure blue to greenishblue shade. They draw very well on to cellulose fibres from a bath containing Glaubers salt. The cellulose dyeings which are also pure blue to greenish-blue in shade only slightly change their shade on the action of copper salts. The disazo dyestuifs according to the present application are fixed very fast to light and washing by the after-coppering process.

The direct cellulose dyeings can be coppered either in the dyebath or in a fresh bath with the usual copper salts, e. g. copper sulphate or copper acetate. The copper out limiting it in any way. Where not otherwise stated, 58 parts of the aminoazo dyestuff from diazotised 5- parts are given as parts by weight and the temperatures (4aminobenzoyl)-amino-2-hydroxybenzene-l-carboxylic are in degrees Centigrade. The relationship of parts by acid and 1-amino-2-carboxymethoxynaphthalene-6-sulweight to parts by volume is as that of kilogrammes to phonic acid are diazotised in the same manner as is delitres. 5 scribed in Example 1 and coupled in the presence of Example 1 COOH OCHiCOOH OH HO- N=N N: I\|T BIT COOH 1.0a am Hag...

N s0=H pyridine with 59.1 parts of the ternary condensation product from 1 mol of cyanuric chloride, 1 mol of 2-(4'-amino- 46.1 parts of the aminoazo dyestuff from diazotised 5- amino-Z-hydroxybenzene-l-carboxylic acid and l-arnino- Z-carboxy-rnethoxynaphthalene-6-sulphonic acid are disphenyl)-amino-2-hydroxynaphthalene 7 sulphonic acid solved at in 1500 parts of water in the presence of a 00 and 2 mol of aminobenzene. The isolated disazo dyestuif little sodium carbonate. A solution of 7.6 parts of sodium dyes cotton and staple fibre in strong blue shades which, nitrite in parts of water is then added and the whole on being treated afterwards with copper salts, have very is poured into 42 parts of hydrochloric acid and 80 good fastness to washing and light. parts of water at 15". After stirring for several hours the If in this example, the 5-(4'-aminobenzoyl)-amino-2- light brown diazo compound is formed, whereupon it is hydroxybenzene-l-carboxylic acid in the aminoazo dyecooled withice to 0-5 stuff is replaced by 5-(3-aminobenzoyl)-amino-2-hy- In the meantime, 65.1 parts of the condensation proddroxybenzene-l-carboxylic acid, by 5-(4'-amino-3-methuct produced in the usual. manner from 1 mol of eyanuric ylbenzoyl)-amino-2-hydroxybenzene-l-carboxylic acid or chloride, 1 mol of 2-(4'-aminophenyl)-amino-5-l1ydroXyby 5-(4-amino-4-methylbenzoyl)-amino-2-hydroxybennaphthalene-7-sulphonic acid, 1 mol of 5-amino-2-hyzene-l-carboxylic acid and otherwise the same procedure droxybenzene-l-carboxylic acid and 1 mol of aminobenis followed, then disazo dyestuffs are obtained the afterzene and parts of sodium carbonate are dissolved in coppered cellulose dyeings of which have a similar shade 1000 parts of water. The solution is cooled to 0-5 and and corresponding fastness properties. stirred with 300 parts by volume of pyridine. The sus- If instead of 2 mols of aminobenzene a cyanuric depension of the diazo compound is poured in at this tem- 3r rivative obtained from the reaction of 1 mol of S-aminoperature. The coupling is complete in a short time. The 0 Z-hydroxybenzene-lcarboxylic acid and 1 mol of aminodisazo dyestuff obtained in this way, when dry, is a dark benzene is used and otherwise the same procedure is folpowder which dissolves in Water with a greenish-blue lowed, disazo dyestufis with similar properties are obshade. It dyes cotton and regenerated cellulose in clear, tained.

Example 3 /C NH- N \N COOH (i)CH2COOH (DH I I 80311 HO -N=N- N=N NH-C C-NH- HOaS NHCO SOsH I s 03H greenish-blue shades. On after-treating with copper salts The aminoazo dyestufi from diazotised 5amino-2-hya dyeing which is only slightly diiferent in colour is obdroxybenzene-l-carboxylic acid and 1-amino-2-carboxytained which has very good fastness to washing and methoxynaphthalene-6-sulphonic acid is diazotised as delight. scribed in Example 1 and in the presence of pyridine cou- If in the above example a cyanuric condensation prodpled with 78.9 parts of the ternary condensation product net is used as azo component which, instead of being profrom 1 mol of cyanuric chloride, 1 mol of 2-(3'-aminoduced from 1 mol of 5-amino-2-hydroxybenzene-l-carbenzoyl) ami'no-5-hydroxynaphthalene-7-sulphonic acid boxylic acid with 1 mol of another amine, is produced for and 2 mols of 3-aminobenzene-1-sulphonic acid. A disazo example from aminobenzene, S-aminobenzene-l-cardyestufi is obtained which dyes cellulose fibres a pure blue boxylic acid, 4-aminobenzene-l-sulphonic acid or 4- shade. The fastness to washing and light is considerably aminobenzene-l-sulphonamide or 1 mol of an aliphatic increased by after-treatment with solutions of copper salts. amine such as, e. g. diethylamine, ethylene diamine or Similar disazo dyestulfs which also dye cellulose materidioxethylamine, then disazo dyestuffs are obtained which al in strong blue shades are obtained if a cyanuric conalso dye cellulose material in clear greenish-blue shades densation product is used in which the 2-(3'-aminobenand have the same good properties. Zoyl)-amino-5-hydroxynaphthalene-7-sulphonic acid is re- If in the aminoazo dyestufl, the l-amino-Z-carboxyplaced by 2-(4'-aminobenzoyl)-amino-5-hydroxynaphthamethoxynaphthalene-6-sulphonic acid is replaced by 1- 1ene-7-sulphonic acid or 2-(4'-aminophenylcarbarnyl)- amino2carboxy-methoxynaphthalene-7 -sulphonic acid amino-5-hydroxynaphthalene-7-sulphonic acid or the 3- and otherwise the same procedure is followed, then disazo aminobenzene l-sulphonic acid is replaced by aminobendyestuffs with similar properties are obtained. zene. In this case also the wet and light fastness proper- Example 2 COOH OCHzCOOH OH HO-O-NH-C O-O-N= N=N- fli ii H033 NEON rr-o CN H-O SOzH mild! .6 ties are considerably improved by after-treatment with lene-7-sulphonic acid or l.-amino-2-carboxymethoxynaph copper salts. 1 v thalene is used instead of l-anrino-Z-carboxymethoxy- Example 4 naphthalene-tS-sulphonic acid, disazo dyestufis are ob- OOOH OCHgOOOH OH 46.1 parts of the aminoazo dyestufi from diazotised 'tained which also dye cellulose material in clear greenish- 5-amino-2-hydroxybenzene-1-carboxy1ic acid and 1-amin0 blue shades. The dyeings have similarly good properties. 2-carboxymethoxynaphthalene!6sulphonic acid are diazoi Example 6 OCHQCOOH OH tised as described in Example 1 and in the presence of 56.5 parts of the aminoazo dyestuflf from diazotised pyridine are coupled with 63.3 parts of the ternary con 3-amino-4-hydroxybenzophenone-3-carboxylic acid and densation product from 1 mol of cyanuric chloride, 1 mol 1-amino-2-carboxymethoxynaphthalene-6-sulphonic acid of 2-(3-aminophenyl)-5"-hydroxy-4.5:1".2-naphthothiare di'azotised as described in Example 1 and coupled in azole-7"-sulphonic acid and 2 mols of amin-obenzene to the presence of pyridine with 59.1 parts of the ternary form the disazo dyestufi. This dyestuff dyes cotton and condensation product from 1 mol of cyanuric chloride, 1 regenerated staple fibre in strong blue shades which on mol of 2-(4'-aminophenyl)-amino-5-hydroxynaphthaleneafter-treatment with copper salts have very good fastness 7-sulphonic acid and 2 mols of aminobenzene. The isoto washing and light. lated di'sazo dyestufi dyes cotton and staple fibre in strong If in this example instead of the 2-(3'-aminophenyl)- blue shades which, when after-treated with copper salts, 5-hydroxy-4.5 l".2"-naphthothiazole-7"-sulphonic acid have very good fastness to washing and light.

in the cyanuric condensation product, 2-(4-arninophenyl- Similar disazo dyestufis which dye cellulose material carbamyl)-amino-5-hydroXynaphthalene-7-sulphonic acid in clear blue shades are obtained if the 3'-amino-4-hyis used, or if 3-arnin0benzene-l-carboxylic acid is used droxy-benzophenone-3-carboxylic acid is replaced by 4- instead of aminobenzene, then disazo dyestufls are'obamino-4-hydroxybenzophenone-3-carboxylic acid or by 4'- tained which, on after-treatment with copper salts, pro- 40 amino 3' methyl 4-- hydroxybenzophenone 3 carduce cellulose dyeings with similar good properties. boxylic acid. In this case too the fastness to light and Example 5 COOH OCHICOOH 0H N 80:11 v 54.1 parts of aminoazo dyestuff from diazotised 5- Washing is considerably improved by copper after-treatamino-3-sulpho-2-hydroxybenzene-l-carboxylic acid and ment. 1-amino-2-carboxymethoxynaphthalene/6-sulphonic acid Example 7 COOE OCHCOOH OH are coupled in the presence of pyridine as described in 38.1 parts of the aminoazo dyestulf from diazotised 5- Exa-mple 1 with 59.1 parts of the ternary condensation amino-2-hydroxybenzene-l-carboxylic acid and l-aminoproduct from 1 mol of cyanuric chloride, 1 mol of 2-(4'- 2-carboxymethoxynaphthalene are diazotised as described aminophenyl) amino 5 hydroxynaphthalene 7 sulin Example 1 and coupled in the presence of pyridine phonic acid and 2 mols of aminobenzene. A disazo dyewith 59.1 parts of the ternary condensation product from stuff is obtained which dyes cellulose fibres a clear blue 1 molof cyanuric chloride, 1 mol of 2-(4-aminophenyl)- shade. The fastness to washing and light is consideramino-S-hydroxynaphthalene-7-sulphonic acid and 2 mols ably increased by after-treatment with copper sulphate of aminobenzene. This dyestutf dyes cellulose material solutions. p p in strong blue shades which, when after-treated with cop- If the 5-amino-3-sulpho-2-hydroxybenzene-l-carboxylic per salts, havevery good fastness to light and washing. acid is replaced by 5-sulpho-3-amino-2-hydroxybenzene-1- If instead of 2 mols of aminobenzene in the eyanuric carboxylic acid or if 1-amino2-carboxymethoxynaphtha- 7 condensation product Zmols of diethylamine or 2 mols of 7 diethanola'mi'ne or 1 rhol of 3-aminobenzene-l-carboxylic 'acid and 1 mol of monoethanolamine or 1 mol of ethylene diamine, are used then disazo dyestuffs are obtained which produce cellulose dyeings with similar good properties when after-treated with copper salts.

Example 8 2 parts of the dyestuif obtained accordin gto Example 1 are dissolved in a dyebath containing 3000 parts of Water and 1 part of soda. 100 parts of cotton are entered at 40-45, the bath is brought to 90-95 Within 30 minutes, 30 parts of sodium sulphate are added and dyeing is performed at this temperature for 45 minutes. At the end of this time, the dyed goods are rinsed cold in the usual Way and after-treated in a fresh bath at 70 for 30 minutes containing 2 parts of copper sulphate and 2 parts of acetic acid. The goods are then rinsed cold and dried. In this way, the cotton is dyed in clear, greenish-blue shades which have very good wet and light fastness properties.

wherein A represents an aromatic radical of the benzene series containing the hydroxyl and carboxyl group in o position to each other, X represents a bridging member selected from the group consisting of NHCO-- and -CO, and linked to nucleus I in other than the o-position, W represents a member selected from the group consisting of H and methyl, n is an integer from 0-1 inclusive, one Y represents hydrogen and the other Y represents a member selected from the group consisting of hydrogen and the sulphonic acid group, Q represents a bridging member selected from the group consisting of NH, NHCO--, NHCO--NH and l and linked to nucleus 11 in other than the o-position, and Z1 and Z2 represent a member selected from the group consisting of lower alkylamino and monocyclic arylamino radicals.

What we claim is: 20 l. A dis'az'o dyestuff having the general formula:

OCHQCOOH 0-21 AX l N N H0 0 0 N=N- N=N A NHC -21 J a w n Hots Q N 2. A disazo dyestufi of the formula: (300E (|)CH1COOH 011 H N r N o 0 011 HO;S- NH-O-NH-( j C-NH-Q-OH 3. A disazo dyestufi of the formula:

- I, N nots- NHO-NH-C (b-NHQ N SOtH 4. A disazo dyestufl? of the formula:

coon I porn'ooon on N N N c NH--so,m1, HO N R T Ho;s NHONH-O CNH 5. A disazo dyestuff of the formula:

COOH ocmooofl on I N N N T t rtms- NHO-NH-u C-NH-O 6. A disazo dyestuff of the formula:

000E OCH=COOH 0H SOaH Anderau Jan. 6, 1942 

1. A DISAZO DYESTUFF HAVING THE GENERAL FORMULA: 